Antiseptic and germicidal composition



Patented July 20, 1937 UNITED sT TEs PATENT OFFICE an'rrsnmc AND GERMICIDAL COM-POSI- TION 1 William E. Austin, New York, N. Y.

No Drawing.

Application July 30, 1934,

Serial No. 737,599

10 Claims.

where R. is phenyl or halogenophenyl; X is any alkyl radical; Y is H or any alkyl radical; and m is 1 or 2.

I have found that under certain conditions to be described more fully, casein forms combinations with phenolic substances, yielding compositions which possess the desirable antiseptic and germicidal qualities of the original phenolic derivatives, and in addition many valuable and desired qualities and characteristics, which constitute a distinct and signal improvement in antisepsis, and antiseptic therapy.

Included in the scope of this invention are the -antiseptic compositions comprising the combinations of casein with primary, secondary or tertiary mono-alkyl phenols; casein with primary, secondary or tertiary mono-alkyl chloro-phenols; casein with 'primary, secondary or tertiary monoalkyl resorcinols; casein with primary, secondary or tertiary mono-alkyl chloro-resorcinols; casein with symmetrical dialkyl resorcinols; casein with asymmetrical dialkyl resorcinols; casein with primary, secondary or tertiary mono-alkyl catecl'iols; casein with primary, secondary or tertiary mono-alkyl chloro-catechols; casein with primary, secondary or tertiary mono-alkyl hydroquinones; casein with primary, secondary or tertiary mono-alkyl chloro-hydroquinones.

Asymmetrical dialkyl resorcinols have been described in my pending application Serial No. 633,086, filed Sept. 14, 1932.

Secondary alkyl resorcinols have been described in my pending application Serial No. 682,270 filed July 26, 1933.

Primary alkyl chloro-resorcinols have been described in my pending application Serial No. 682,271 filed July 26, 1933.

Secondary alkyl chloro-resorcinols have been described in my pending application Serial No. 682,272 filed July 26, 1933.

Tertiary alkyl chloro-resorcinols, tertiary alkyl chloro-catechols, and tertiary alkyl chloro-hydroquinones have all been described in my pending application Serial No. 715,495 filed Mar. 14, 1934.

The other phenolic compounds have been described elsewhere, arid are readily available.

-The new compositions of the present invention may be prepared in a simple, eiflcient and inexpensive manner, by mixing a hot, neutral,

aqueous suspension of the desired phenolic sub-- dery amorphous substances, varying in color from pale cream to yellow-brown. While the exact nature of the casein-phenol compounds has not been determined, the combination seems to be more intimate than a simple mixture. Extraction of any of the compounds at ordinary room temperatures, with alcohol (ethyl) removes only a part of the phenolic constituent, although alcohol is one of the best solvents for the phenolic substances. This alcoholic extract may be used as a means of identifying the particular caseinphenol composition, by determining the boiling point, or melting point of the extracted phenol, or by other customary tests.

The casein-phenol compositions are all homogeneous, stable products, which are admirably adapted for use in internal'as well as external antiseptic and germicidal therapeutic administration. The compositions may be used as dusting powders, wet-packs or compresses for external antisepsis; or in powder form, and if desired, compressed into tablets, pellets or pills for internal use. 7

In medical practise, phenolic substances of the type above indicated have been employed hitherto inthe form of dilute solutions in alcohol, glycerine, glyc'ols or oils, mainly for external treatment. In higher concentrations, solutions in oil encased in capsules have been used in internal therapy. The compositions of casein with phenols of the present invention afford many advantages; over the previously employed solutions of antiseptic phenols, especially for internal treatment. The casein compounds are much simpler and cheaper to prepare. They can be administered with greater ease, convenience, .and less objection or form, as powders, pills or tablets. Much higher concentrations of the desired phenolic substance can be used in the casein compositions, without any escharotic or irritant action on the mucous tissues of the oral and alimentary tracts. The use of' relatively high concentrations of the phenolic constituentis desirable in the treatment of certain intestinal ailments such as abscesses, ulcers, putrefactive conditions, parasitic organisms of animal or vegetable nature, and in general antisepsis of the urinary and alimentary tracts. The dosage naturally depends on theparticular condition to be treated and therefore must be left to the physician's discretion.

Because of the fact thatthe antiseptic and germicidal compositions of the present invention are apparently rather intimate combinations of casein with the respective phenolic substances, possibly even true chemical compounds, the desired antiseptic and other beneficial properties phenols concerned. This may be done either by mixing the separate casein compositions of the respective phenols, or by preparing a casein composition containing the phenols together.

The following examples. illustrate the method of preparing the compositions of the present invention: Y 1

1. 10 grams of ethyl-hexyl resorcinol are mixed with 500 cc. of hot water (75 C.) While stirring constantly,v 25 grams of granular, edible casein are added quickly. Reaction takes place with disappearance of the phenol from the aqueous portion of the mixture, and simultaneous darkening of the casein. Stirring is continued,and the temperature maintained at 75, until the product coalesces into a heavy lump. Allow to cool to room temperature, and filter. (The filtrate when tested shows complete absence of phenolic substance.) Thefilter cake is air dried, yielding a brownish granular mass, which can be easily powdered.

2. 25 grams p-ter.-amyl phenol are added to 500 cc. water, and heated to about C. To this mixture is added while stirring, 25 grams granular casein, and the stirring is continued until the mass coagulates. It is then filtered off, and air dried, yielding a pale cream colored mass. easily powdered.

3. 5 grams of sec. octyl chloro-resorcinol (derived from methyl hexyl 'carbinol) and 5 grams hexyl resorcinol are mixed with 500 cc. water at 75C., and while stirring vigorously 50 grams of casein are added, and stirring continued and temperature kept at 75 C. until the mass coagulates. After cooling to room temperature, the mass is filtered ofl, and air dried. A slightly yellowish granular mass is obtained, which crumbles easily.

The following compositions have been made 2,087,588 resistance of the patient, because they are in solid by the method described in the above examples: Parts Casein parts p-ter. amyl phenol M..P.

92-93'C 25. Casein 100 parts p-ter. amyl phenol 100 5 Casein 100 parts p-sec. hexyl phenol B. P.

Casein 100 parts n-hexyl resorcinol M. P. 15

ST-69C I 25 Casein 100 parts n-hexyl resorcinol 100 Casein 100 parts n-heptyl resorcinol M. P.

'73-'75C 40 Casein 100 parts n-hexyl chlororesorcinol B.- 20 165-175 C./4 mm 40- Casein 100 parts n-heptylchlororesorcinol B.

201-03-C./15 mm 25 Casein 100 parts n-heptylchlororesorcinol--- 100 Casein 100 parts n-octyl chlororesorcinol B. I 25 185-95 C./5 mm 100 Casein 100 parts sec. .hexyl resorcinol B. 1'70-78 C./7 mm 40 Casein 100 parts sec. heptylresorcinol B.

155-65C./ 3 mm r. L 25 Casein 100 parts sec. octylresorcinol B. 190- 2l0 C./1 mm 100 Casein 100 parts sec. hexylchlororesorcinol B.

-170'-90,C./4 mm. 10 Casein'100 parts sec. heptyl chlororesorcinol 35 B. -50 C./4 mm 40' Casein 100 parts sec. octylchlororesorcinol B.

160-75" C./5 mm 5 Casein 100 parts sec. dctylchlororesorcinol--- 100 Casein 100 parts di-iscbutyl resorcinol M. i 40 101-2 C 40 Casein 100 parts ter. amyl chlororesorcinol B.

-50" C./7 mm 25 Casein 100 parts ter. butylchlororesorcinol B. 1

135-40" c./5 mm 4o 45 Casein 100 parts di-isobutylchlororesorcinol Casein 100 parts di-isobutylchlororesorcinol 100 Casein 100 parts ter. amyl chlorohydroqui- Casein 100 parts ethyl-hexyl resorcinol 25 Casein 100 parts ethyl-hexyl resorcinol 100 Casein 100 parts methyl-hexyl resorcinol B.

170-80 c./5 mm 40 Casein 100 parts methyl-heptyl resorcinol B.

172-80 C./4-5 mm 10 Casein 100 parts methyieheptyl resorcinol 100 Casein 100 parts methyl-heptyl resorcinoL- 25 7o Casein 100 parts sec. octyl p-chlorophenol B.

-60", C./3 mm 40 I claim: 1 1. Antiseptic and germicidal compositions preparedby treating in neutral, aqueous medium .15

at approximately C., casein with a phenol oi the general formula where' R is phenyl or halogenophenyl; x is any alkyl radical; Y is H or any alkyl radical; and m is 1 or 2.

2. Antiseptic and germicidal compositions prepared by treating in neutral. aqueous medium at approximately 75 C., casein with 5% to of its weight of a phenol of the general formula where R is phenyl or halogenophenyl; x is any alkyl radical; Y is H or any alkyl radical; and m is 1 or 2; and separating the coagulated compound after cooling, and drying at ordinary temperatures.

3. The method of preparing antiseptic and germicidal compositions, which consists in treating in neutral aqueous medium at approximately 75 0., casein with 5% to 100% of its weight of a phenol oi the general formula Y where R is phenyl or halogenophenyl; In any alkyl radical; Y is H or any alkyl radical; and m is 1 or 2; separating the coagulated compound after cooling, and drying at ordinary temperatures.

4. Antiseptic and germicidal compositions 'prepared by treating in neutral aqueous medium at approximately 75 0., casein with 5% to 100% of its weight 01' sec. octyl chloro-resorcinoi, sepmicidal compositions which consists in treating in neutral aqueous medium, at approximately 75 C. casein with a phenolic substance of the general formula where R is phenyl or halogenophenyl; X is any alkyl radical; Y is H or any alkyl radical; and m is 1 or 2; and separating the coagulated compound.

6. Antiseptic and germicidal compositions prepared by treating casein with sec. octyl chlororesorcinol in neutral aqueous medium at approximately 75 C.

' 7. Antiseptic and germicidal compositions prepared by treating casein with ethyl-hexyl resorcinol in neutral aqueous medium at approximately 75 C.

8. Antiseptic and germicidal compositions prepared by treating casein with p-ter. amyl phenol in neutral aqueous medium at approximately 75 C.

9. Antiseptic and germicidal compositions-prepared by treating casein with 5% to 100% of weight of ethyl-hexyl resorcinol in neutral aque-' ous medium at approximately 75 0., separating the coagulated compound after cooling and drying at ordinary temperatures.

10. Antiseptic and germicidal compositions prepared by treating casein with 5% to 100% of its weight or p-ter. amyl phenol in neutral aqueous medium at approximately 75 C., separating the coaguiated compound after cooling and drying at ordinary temperatures.

wnum a. Aus'nu. 

